EP0888296B1 - Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition - Google Patents

Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition Download PDF

Info

Publication number
EP0888296B1
EP0888296B1 EP97908265A EP97908265A EP0888296B1 EP 0888296 B1 EP0888296 B1 EP 0888296B1 EP 97908265 A EP97908265 A EP 97908265A EP 97908265 A EP97908265 A EP 97908265A EP 0888296 B1 EP0888296 B1 EP 0888296B1
Authority
EP
European Patent Office
Prior art keywords
metal salts
formula
slightly water
soluble
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97908265A
Other languages
German (de)
French (fr)
Other versions
EP0888296A1 (en
Inventor
Eberhard Knaak
Joachim Heyer
Marlies Dr. Kleinfeld
Christel Van Wijngaarden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BLASBERG OBERFLAECHENTECHNIK GMBH
Original Assignee
Blasberg Oberflachentechnik GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Blasberg Oberflachentechnik GmbH filed Critical Blasberg Oberflachentechnik GmbH
Publication of EP0888296A1 publication Critical patent/EP0888296A1/en
Application granted granted Critical
Publication of EP0888296B1 publication Critical patent/EP0888296B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/18—Dithiocarboxylic acids

Definitions

  • the present invention relates to metal salts of the formula I which are sparingly soluble in water in which R 1 and R 2 are the same or different and are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, M is the cation of a metal which forms sparingly soluble sulfides in water and n is 1 or 2, and mixtures thereof, processes for Production of the same and its use as a gloss additive for the electrolytic deposition of metals.
  • Silver deposits are known in which sulfur-containing compounds such as carbon disulfide (and other sulfur-containing Compounds) with ketones and strong alkali and then acidified, precipitated and possibly after redissolution with alkali and after precipitation with mineral acid was used as an additive to silver baths. These silver baths formaldehyde or Turkish red oil were mostly added.
  • the new metal salts are effective in concentrations from 0.005 to 0.3 g / l. Apparently, the remaining components of the electrolytes increase the solubility of the poorly soluble metal salts so that they go back into solution.
  • the process for the preparation of the sparingly soluble metal salts of the formula I is characterized in that carbon disulfide with ketones of the formula II in which R 1 and R 2 have the meaning given above, optionally with the addition of non-aqueous, inert solvents with strong alkali, preferably potassium hydroxide, whereupon by adding aqueous solutions of metal salts of the metals M, the poorly water-soluble metal salts of the formula I. be canceled.
  • the molar ratio between carbon disulfide and the ketones is not critical. It is always important to have a sufficient amount of Alkali hydroxide.
  • the precipitation of the poorly soluble metal salts is also unproblematic, since it is sufficient to use the water-soluble Metal salts in aqueous solution with the reaction mixture mix.
  • the poorly soluble in water Metal salts of formula I precipitate out and can be separated in the usual way. If you want, you can washed and dried and stored in this form and be used later.
  • Example 1 1 mol of acetone is mixed with 0.65 mol of carbon disulfide and 1.35 mol Potassium hydroxide implemented.
  • the liquid Phase with 20 ml silver nitrate solutions (1 molar) the sparingly soluble Silver salt separated. It becomes a glossy electrolyte for silver added, which 0.1 to 1 g / l of the silver salt contains and 10 ml / l of a formaldehyde-naphthylsulfonic acid condensation product as the primary brightener.
  • the remaining solid is homogenized with water and provided with acid, whereby free acid fails.
  • the precipitated solid is quickly redissolved in alkali solution, precipitated again with acid and dried.
  • the solid is dissolved in potassium hydroxide and in cyanide silver electrolytes added along with the salt according to the invention.
  • both the liquid phase and the solid phase is mixed with water and then with silver nitrate the difficultly soluble silver salt precipitates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Detergent Compositions (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

PCT No. PCT/EP97/01389 Sec. 371 Date Sep. 16, 1998 Sec. 102(e) Date Sep. 16, 1998 PCT Filed Mar. 20, 1997 PCT Pub. No. WO97/35840 PCT Pub. Date Oct. 2, 1997The slightly water-soluble metal salts having the formula I wherein R1 and R2 are the same or different and represent hydrogen or a lower alkyl group of from 1 to 3 carbon atoms, M is the cation of a metal which forms slightly water-soluble sulfides, and n means 1 or 2, and mixtures thereof are prepared by reacting carbon disulfide with ketones having the formula II: optionally with the addition of non-aqueous inert solvents, in the presence of strong alkali, preferably potassium hydroxide, followed by precipitation of the slightly water-soluble metal salts of formula I by the addition of aqueous solutions of metal salts of the metals M. They are used as gloss additives to electrolytic baths.

Description

Gegenstand der vorliegenden Erfindung sind in Wasser schwerlösliche Metallsalze der Formel I

Figure 00010001
in der R1 und R2 gleich oder verschieden sind und Wasserstoff oder eine niedere Alkylgruppe mit 1 bis 3 Kohlenstoffatomen bedeuten, M das Kation eines Metalls ist, welches in Wasser schwerlösliche Sulfide bildet und n 1 oder 2 bedeutet, sowie Gemische derselben, Verfahren zur Herstellung derselben und ihre Verwendung als Glanzzusatz zur elektrolytischen Abscheidung von Metallen.The present invention relates to metal salts of the formula I which are sparingly soluble in water
Figure 00010001
in which R 1 and R 2 are the same or different and are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, M is the cation of a metal which forms sparingly soluble sulfides in water and n is 1 or 2, and mixtures thereof, processes for Production of the same and its use as a gloss additive for the electrolytic deposition of metals.

Aus der DE-PS-885 036 ist ein Verfahren zur Erzeugung glänzender Silberniederschläge bekannt, bei welchem schwefelhaltige Verbindungen wie Schwefelkohlenstoff (und andere schwefelhaltige Verbindungen) mit Ketonen und starkem Alkali umgesetzt und danach angesäuert, ausgefällt und gegebenenfalls nach Wiederauflösung mit Alkali und nach erneuter Ausfällung mit Mineralsäure als Zusatz zu Silberbädern verwendet wurde. Diesen Silberbädern wurden meist noch Formaldehyd oder Türkischrotöl zugesetzt.From DE-PS-885 036 a method for producing glossy is Silver deposits are known in which sulfur-containing compounds such as carbon disulfide (and other sulfur-containing Compounds) with ketones and strong alkali and then acidified, precipitated and possibly after redissolution with alkali and after precipitation with mineral acid was used as an additive to silver baths. These silver baths formaldehyde or Turkish red oil were mostly added.

Aus der DE-PS 27 31 595 ist bekannt, daß derartige Bäder verbessert werden können, wenn die Kondensationsprodukte aus Keton, Alkalihydroxid und Schwefelkohlenstoff mit wasserlöslichen Salzen von Naphthalinsulfonsäure-Formaldehyd-Kondensationsprodukten versetzt wurden. Insbesondere bei Zusatz zu cyanidischen Silberbädern ist es möglich, so hochglänzende Silberniederschläge herzustellen.From DE-PS 27 31 595 it is known that such baths are improved if the condensation products from ketone, Alkali hydroxide and carbon disulfide with water soluble Salts of naphthalenesulfonic acid-formaldehyde condensation products were transferred. Especially when added to cyanide It is possible for silver baths, such as high-gloss silver deposits to manufacture.

Bereits aus den Arbeiten von Apitzsch Berichte 37, 1599 (1904) und Berichte 38, 2888 (1905) sowie Berichte 41, 4028 (1908) war bekannt, daß bei der Kondensation von Ketonen mit Schwefelkohlenstoff und anschließender Ansäuerung cyclische Verbindungen der Formel

Figure 00020001
entstehen. Bisher ist man davon ausgegangen, daß diese cyclischen Verbindungen verantwortlich sind für die Glanzbildung in Silberbädern. Massenspektroskopische Untersuchungen von derartigen Reaktionsansätzen haben jetzt bestätigt, daß tatsächlich die cyclischen Verbindungen entstehen. Man hat in der Vergangenheit versucht, insbesondere diese cyclische Fraktion anzureichen und den Glanzbildnern zuzusetzen.Already from the work of Apitzsch reports 37, 1599 (1904) and reports 38, 2888 (1905) and reports 41, 4028 (1908) it was known that in the condensation of ketones with carbon disulphide and subsequent acidification, cyclic compounds of the formula
Figure 00020001
arise. So far it has been assumed that these cyclic compounds are responsible for the gloss formation in silver baths. Mass spectroscopic investigations of such reaction batches have now confirmed that the cyclic compounds are actually formed. In the past, attempts have been made to enrich this cyclic fraction in particular and to add it to the brighteners.

Eingehende Untersuchungen der Anmelderin haben jetzt weiterhin zu dem überraschenden Ergebnis geführt, daß nicht diese cyclischen Verbindungen für die Glanzbildung verantwortlich sind, sondern die als Nebenprodukte vor dem Ansäuern entstehenden Verbindungen der Formel I, in denen jedoch M das Kation eines Metalls ist, welches in Wasser gutlösliche Sulfide bildet. Bei allen bisher beschriebenen und praktizierten Methoden zur Herstellung der Kondensationsprodukte von Ketonen mit Schwefelkohlenstoff sind entweder die wasserlöslichen Alkalisalze oder die durch Säuren ausfällbaren schwerlöslichen cyclischen Verbindungen entstanden.In-depth investigations by the applicant have now continued led to the surprising result that not these cyclic Compounds are responsible for the gloss formation, but the by-products that arise before acidification Compounds of formula I, in which, however, M is the cation of a Is metal, which forms readily soluble sulfides in water. At all previously described and practiced methods for Manufacture of condensation products of ketones with carbon disulphide are either the water-soluble alkali salts or the poorly soluble cyclic compounds which can be precipitated by acids emerged.

Es wurde jetzt weiterhin festgestellt, daß diese erfindungsgemäßen Nebenprodukte stabilisiert und in unzersetzter Form abgetrennt werden können, wenn sie als in Wasser schwerlösliche Salze ausgefällt werden. Schwerlösliche Salze bilden vor allem die Metalle, die auch in Wasser schwerlösliche Sulfide bilden. Neben Silber handelt es sich somit insbesondere um Kupfer, Blei, Wismut, Antimon, Cobalt, Eisen, Zink, Palladium, Molybdän, Zinn und Gold.It has now also been found that these according to the invention By-products stabilized and separated in undecomposed form if they are considered sparingly soluble in water Salts are precipitated. Above all, poorly soluble salts form the metals that form sulfides that are sparingly soluble in water. In addition to silver, it is therefore especially copper, lead, Bismuth, antimony, cobalt, iron, zinc, palladium, molybdenum, tin and gold.

Es wurde weiterhin festgestellt, daß diese schwerlöslichen Metallsalze nicht nur wesentlich stabiler sind als die bisher als instabil beobachteten Nebenprodukte oder cyclischen Verbindungen, sondern daß darüber hinaus diese schwerlöslichen Metallsalze hervorragend geeignet sind, als Glanzzusatz zu wirken. Dabei kann sogar auf die üblichen Primärglanzbildner wie Türkischrotöl sowie die Kondensationsprodukte von Formaldehyd mit Naphthalinsulfonsäuren verzichtet werden. Auf alle Fälle erhält man mit und ohne Zusatz dieser bekannten primären Glanzbildner erheblich bessere Glanzschichten von Silber. Anscheinend sind diese schwerlöslichen Metallsalze in der Lage, in Elektrolyten soweit wieder in Lösung zu gehen, daß sie die Funktion eines Glanzbildners übernehmen können.It has also been found that these are sparingly soluble Metal salts are not only much more stable than those previously by-products or cyclic compounds observed as unstable, but also that these poorly soluble metal salts are ideally suited to act as a gloss additive. You can even use the usual primary gloss agents such as Turkish red oil as well as the condensation products of formaldehyde Naphthalenesulfonic acids are dispensed with. Definitely receives one with and without the addition of these known primary brighteners significantly better gloss layers of silver. Apparently are these poorly soluble metal salts are able to be found in electrolytes so far to go back into solution that they have the function of a Brightener can take over.

Die neuen Metallsalze sind bereits in Konzentrationen von 0,005 bis 0,3 g/l wirksam. Anscheinend wird durch die übrigen Bestandteile der Elektrolyte die Löslichkeit der schwerlöslichen Metallsalze so erhöht, daß sie wieder in Lösung gehen. Das Verfahren zur Herstellung der schwerlöslichen Metallsalze der Formel I ist dadurch gekennzeichnet, daß Schwefelkohlenstoff mit Ketonen der Formel II

Figure 00030001
in denen R1 und R2 die oben angegebene Bedeutung haben, gegebenenfalls unter Zusatz von nichtwäßrigen, inerten Lösungsmitteln mit starkem Alkali, vorzugsweise Kaliumhydroxid umgesetzt wird, woraufhin durch Zugabe von wäßrigen Lösungen von Metallsalzen der Metalle M, die in Wasser schwerlöslichen Metallsalze der Formel I ausgefällt werden.The new metal salts are effective in concentrations from 0.005 to 0.3 g / l. Apparently, the remaining components of the electrolytes increase the solubility of the poorly soluble metal salts so that they go back into solution. The process for the preparation of the sparingly soluble metal salts of the formula I is characterized in that carbon disulfide with ketones of the formula II
Figure 00030001
in which R 1 and R 2 have the meaning given above, optionally with the addition of non-aqueous, inert solvents with strong alkali, preferably potassium hydroxide, whereupon by adding aqueous solutions of metal salts of the metals M, the poorly water-soluble metal salts of the formula I. be canceled.

Das Mol-Verhältnis zwischen Schwefelkohlenstoff und den Ketonen ist unkritisch. Wichtig ist stets eine ausreichende Menge an Alkalihydroxid. Die Ausfällung der schwerlöslichen Metallsalze ist ebenfalls unproblematisch, da es genügt, die wasserlöslichen Metallsalze in wäßriger Lösung mit dem Reaktionsansatz zu vermischen. Die Mengenverhältnisse und Verfahrensbedingungen scheinen einen gewissen Einfluß zu haben auf das Mengenverhältnis der Substanzen, in denen n = 1 und n = 2 ist. Meist fallen beide Substanzen nebeneinander an. Die in Wasser schwerlöslichen Metallsalze der Formel I fallen aus und können in üblicher Weise abgetrennt werden. Gewünschtenfalls können sie gewaschen und getrocknet werden und in dieser Form auch gelagert und später verwendet werden.The molar ratio between carbon disulfide and the ketones is not critical. It is always important to have a sufficient amount of Alkali hydroxide. The precipitation of the poorly soluble metal salts is also unproblematic, since it is sufficient to use the water-soluble Metal salts in aqueous solution with the reaction mixture mix. The proportions and process conditions seem to have some influence on the quantity ratio of substances in which n = 1 and n = 2. Most of time both substances occur side by side. The poorly soluble in water Metal salts of formula I precipitate out and can be separated in the usual way. If you want, you can washed and dried and stored in this form and be used later.

Als Zusatz zu Glanzelektrolyten ist es auch möglich, die roh gefällten Niederschläge ohne weitere Reinigung und Trocknung zu verwenden, da die schwerlöslichen Metallsalze der Formel I auch in dieser Form ausreichend stabil sind.As an additive to glossy electrolytes it is also possible to use the raw Precipitated precipitation without further cleaning and drying to use because the poorly soluble metal salts of formula I are also sufficiently stable in this form.

In den nachfolgenden Beispielen sind die Salze und ihre Herstellung näher erläutert.In the examples below are the salts and their preparation explained in more detail.

Beispiel 1example 1

1 mol Methylethylketon wird mit 0,65 mol Schwefelkohlenstoff und 1,35 mol Kaliumhydroxid am Rückfluß erhitzt, wodurch die Reaktionstemperatur etwa auf den Siedepunkt von Schwefelkohlenstoff gebracht wird. Nach ca. 2 bis 3 Stunden Reaktionszeit läßt man das Reaktionsgemisch abkühlen, trennt die überstehende flüssige Phase vom Feststoff ab und fällt aus dieser flüssigen Phase mit wäßriger Silbersalzlösung das schwerlösliche Silbersalz aus. Dieses kann gewaschen und getrocknet werden. Der Niederschlag kann auch unmittelbar in 1 %iger cyanidischer Lösung wiederaufgelöst und einem Silberelektrolyten als Glanzbildner zugesetzt werden. Es genügen 0,05 bis 0,3 g/l dieses Silbersalzes als Zusatz zum Glanzelektrolyten.1 mol of methyl ethyl ketone is mixed with 0.65 mol of carbon disulphide and 1.35 mol of potassium hydroxide is heated to reflux, thereby the Reaction temperature approximately to the boiling point of carbon disulfide brought. After a reaction time of approx. 2 to 3 hours the reaction mixture is allowed to cool, the supernatant is separated liquid phase from the solid and falls from this liquid Phase with aqueous silver salt solution the poorly soluble silver salt out. This can be washed and dried. The Precipitation can also occur immediately in 1% cyanide Solution redissolved and a silver electrolyte as a brightener be added. 0.05 to 0.3 g / l of this is sufficient Silver salt as an additive to the bright electrolyte.

Beispiel 2Example 2

1 mol Aceton wird mit 0,65 mol Schwefelkohlenstoff und 1,35 mol Kaliumhydroxid umgesetzt. Wie in Beispiel 1 wird aus der flüssigen Phase mit 20 ml Silbernitratlösungen (1 molar) das schwerlösliche Silbersalz abgetrennt. Es wird einem Glanzelektrolyten für Silber zugesetzt, welcher 0,1 bis 1 g/l des Silbersalzes enthält sowie 10 ml/l eines Formaldehyd-Naphthylsulfonsäure-Kondensationsproduktes als primären Glanzbildner.1 mol of acetone is mixed with 0.65 mol of carbon disulfide and 1.35 mol Potassium hydroxide implemented. As in Example 1, the liquid Phase with 20 ml silver nitrate solutions (1 molar) the sparingly soluble Silver salt separated. It becomes a glossy electrolyte for silver added, which 0.1 to 1 g / l of the silver salt contains and 10 ml / l of a formaldehyde-naphthylsulfonic acid condensation product as the primary brightener.

Beispiel 3Example 3

1 mol Methylethylketon, 0,65 mol Schwefelkohlenstoff und 1,35 mol Kaliumhydroxid werden miteinander umgesetzt. Die flüssige Phase wird mit 25 ml Silbernitratlösung ausgefällt. Der Niederschlag wird in Mengen von 0,01 g/l einem Glanzelektrolyten zugesetzt, welcher 1 ml/l Formaldehyd-Naphthylsulfonsäure-Kondensationsprodukt als primären Glanzbildner enthält.1 mol of methyl ethyl ketone, 0.65 mol of carbon disulfide and 1.35 mol of potassium hydroxide are reacted with one another. The liquid phase is precipitated with 25 ml silver nitrate solution. The precipitate becomes a gloss electrolyte in amounts of 0.01 g / l added which 1 ml / l formaldehyde-naphthylsulfonic acid condensation product contains as a primary brightener.

Beispiel 4Example 4

In analoger Weise wie in Beispiel 3 beschrieben, wird ein Silberglanzelektrolyt hergestellt, welcher mit 10 ml/l Türkischrotöl versetzt ist.In a manner analogous to that described in Example 3, a Silver electrolyte, which with 10 ml / l Turkish red oil is offset.

Beispiel 5Example 5

0,15 mol Methylethylketon werden mit 0,6 mol Schwefelkohlenstoff und 0,6 mol KOH umgesetzt. Aus der flüssigen Phase wird mit Silbernitratlösung das Silbersalz ausgefällt.0.15 mol of methyl ethyl ketone with 0.6 mol of carbon disulfide and reacted 0.6 mol KOH. The liquid phase becomes with Silver nitrate solution precipitated the silver salt.

Zum Vergleich wird der verbleibende Feststoff mit Wasser homogenisiert und mit Säure versehen, wobei freie Säure ausfällt. Der ausgefallene Feststoff wird rasch in Alkalilösung wiederaufgelöst, erneut mit Säure ausgefällt und getrocknet. Der Feststoff wird in Kaliumhydroxid gelöst und als Grundglänzer in cyanidischen Silberelektrolyten zugesetzt zusammen mit dem erfindungsgemäßen Salz.For comparison, the remaining solid is homogenized with water and provided with acid, whereby free acid fails. The precipitated solid is quickly redissolved in alkali solution, precipitated again with acid and dried. The solid is dissolved in potassium hydroxide and in cyanide silver electrolytes added along with the salt according to the invention.

Beispiel 6Example 6

In einem weiteren Ansatz wird sowohl die flüssige Phase als auch die feste Phase mit Wasser verrührt und dann hieraus mit Silbernitrat das schwerlösliche Silbersalz gefällt.In another approach, both the liquid phase and the solid phase is mixed with water and then with silver nitrate the difficultly soluble silver salt precipitates.

Claims (4)

  1. Slightly water-soluble metal salts having the formula I
    Figure 00090001
    wherein R1 and R2 are the same or different and represent hydrogen or a lower alkyl group of from 1 to 3 carbon atoms, M is the cation of a metal which forms slightly water-soluble sulfides, and n means 1 or 2; and mixtures thereof.
  2. A process for the preparation of slightly water-soluble metal salts having the formula I
    Figure 00090002
    wherein R1 and R2 are the same or different and represent hydrogen or a lower alkyl group of from 1 to 3 carbon atoms, M is the cation of a metal which forms slightly water-soluble sulfides, and n means 1 or 2; and mixtures thereof;
    characterized in that carbon disulfide is reacted with ketones having the formula II:
    Figure 00100001
    wherein R1 and R2 have the same meaning as above, optionally with the addition of non-aqueous inert solvents, in the presence of strong alkali, preferably potassium hydroxide, followed by precipitation of the slightly water-soluble metal salts of formula I by the addition of aqueous solutions of metal salts of the metals M.
  3. Use of the slightly water-soluble metal salts of formula I as gloss additives to electrolytic silver plating baths.
  4. The use according to claim 3, characterized in that said metal salt which is added to electrolytic silver plating baths as a gloss additive is a silver salt.
EP97908265A 1996-03-23 1997-03-20 Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition Expired - Lifetime EP0888296B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19611565A DE19611565C1 (en) 1996-03-23 1996-03-23 Stable, hardly water-soluble metal acyl-thio-carboxylate(s)
DE19611565 1996-03-23
PCT/EP1997/001389 WO1997035840A1 (en) 1996-03-23 1997-03-20 Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition

Publications (2)

Publication Number Publication Date
EP0888296A1 EP0888296A1 (en) 1999-01-07
EP0888296B1 true EP0888296B1 (en) 2000-12-20

Family

ID=7789231

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97908265A Expired - Lifetime EP0888296B1 (en) 1996-03-23 1997-03-20 Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition

Country Status (15)

Country Link
US (1) US5981793A (en)
EP (1) EP0888296B1 (en)
JP (1) JP3777401B2 (en)
KR (1) KR100443075B1 (en)
AT (1) ATE198193T1 (en)
CA (1) CA2249533A1 (en)
DE (2) DE19611565C1 (en)
DK (1) DK0888296T3 (en)
ES (1) ES2153651T3 (en)
GR (1) GR3035233T3 (en)
HK (1) HK1015356A1 (en)
MY (1) MY116402A (en)
PT (1) PT888296E (en)
TW (1) TW502038B (en)
WO (1) WO1997035840A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1788632A (en) * 1928-07-13 1931-01-13 Du Pont Process of making organic sulphur compounds
BE505842A (en) * 1950-09-15
DE2731595C3 (en) * 1977-07-13 1984-06-28 G. P. - Chemie GmbH, 5650 Solingen Use of a combination of brighteners in cyanide silver baths
FR2504131B1 (en) * 1981-04-15 1988-03-04 Elf Aquitaine PROCESS FOR PRODUCING ORGANIC DITHIOACIDS AND THEIR APPLICATION

Also Published As

Publication number Publication date
ES2153651T3 (en) 2001-03-01
US5981793A (en) 1999-11-09
PT888296E (en) 2001-03-30
TW502038B (en) 2002-09-11
GR3035233T3 (en) 2001-04-30
HK1015356A1 (en) 1999-10-15
KR100443075B1 (en) 2004-12-03
DE59702787D1 (en) 2001-01-25
MY116402A (en) 2004-01-31
DE19611565C1 (en) 1997-07-10
ATE198193T1 (en) 2001-01-15
WO1997035840A1 (en) 1997-10-02
DK0888296T3 (en) 2001-07-23
KR20000004929A (en) 2000-01-25
JP3777401B2 (en) 2006-05-24
CA2249533A1 (en) 1997-10-02
EP0888296A1 (en) 1999-01-07
JP2000507942A (en) 2000-06-27

Similar Documents

Publication Publication Date Title
DE2039831B2 (en) Acid bath for the galvanic deposition of shiny copper coatings
EP0888296B1 (en) Metallic salts which are difficult to dissolve in water, a process for their production, and their use as brighteners in electrolytic metal deposition
DE1795344B2 (en) PROCESS FOR THE PREPARATION OF 3-AMINOISOTHIAZOLS
DE2731595C3 (en) Use of a combination of brighteners in cyanide silver baths
DE2215737A1 (en) Nickel bath
DE1793558C3 (en) Coumarin derivatives and processes for their preparation
DE3149653C2 (en)
DE564215C (en) Process for the preparation of thio derivatives of phenols
DE894994C (en) Process for the production of aliphatic mercury ketone compounds
DE2008874A1 (en) Pyrimidine derivs from urea and beta-keto - esters
DE614801C (en) Process for the electrolytic deposition of metals of the platinum group
DE65236C (en) Process for the preparation of two p-amidophenol disulfonic acids
DE721724C (en) Process for the preparation of asymmetric thiuram monosulfides
DE222195C (en)
DE568943C (en) Process for the representation of asymmetrical arsenic compounds
DE1518017C3 (en) S-Mercapto-i ^ -dithiacyclopenten-Sthione, process for their preparation and their use
DE1696082A1 (en) Process for the electrolytic deposition of semi-glossy nickel deposits
DE1273529B (en) Process for the preparation of diorganotin S, O-mercapto-acylates
DE651251C (en) Process for the production of yellow lead chromates with high lightfastness
DE2614825B2 (en) Process for the preparation of aminonitrophenols
DE952802C (en) Process for the production of vinyl compounds
DE825406C (en) Process for the production of nitrogen-containing thioethers
DE940555C (en) Combat fungi and other microorganisms
DE2419814C3 (en) Sulphite-containing electroplating bath for the deposition of palladium and palladium alloys
EP0813518B1 (en) Process for preparing alpha,beta-diaminoacrylnitriles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980825

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20000214

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

REF Corresponds to:

Ref document number: 198193

Country of ref document: AT

Date of ref document: 20010115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: SCHMAUDER & PARTNER AG PATENTANWALTSBUERO

Ref country code: CH

Ref legal event code: EP

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: BLASBERG OBERFLAECHENTECHNIK GMBH

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 59702787

Country of ref document: DE

Date of ref document: 20010125

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: BLASBERG OBERFLAECHENTECHNIK GMBH

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2153651

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20010222

ET Fr: translation filed
REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20001221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010331

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20020329

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20030313

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20030321

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20030324

Year of fee payment: 7

Ref country code: DK

Payment date: 20030324

Year of fee payment: 7

Ref country code: CH

Payment date: 20030324

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20030325

Year of fee payment: 7

Ref country code: IE

Payment date: 20030325

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030326

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040320

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040320

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040320

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

BERE Be: lapsed

Owner name: *BLASBERG OBERFLACHENTECHNIK G.M.B.H.

Effective date: 20040331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041015

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20040930

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070321

EUG Se: european patent has lapsed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20060314

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20080328

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20080318

Year of fee payment: 12

Ref country code: GB

Payment date: 20080320

Year of fee payment: 12

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090320

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20091001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090320

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090321

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090321

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20160321

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160330

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160324

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59702787

Country of ref document: DE